EP0328507B1 - Process for preparing catalysts containing a metal of the platinum group, and uses thereof - Google Patents
Process for preparing catalysts containing a metal of the platinum group, and uses thereof Download PDFInfo
- Publication number
- EP0328507B1 EP0328507B1 EP89870026A EP89870026A EP0328507B1 EP 0328507 B1 EP0328507 B1 EP 0328507B1 EP 89870026 A EP89870026 A EP 89870026A EP 89870026 A EP89870026 A EP 89870026A EP 0328507 B1 EP0328507 B1 EP 0328507B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- metal
- comprised
- weight
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
- C07C5/41—Catalytic processes
- C07C5/415—Catalytic processes with metals
- C07C5/417—Catalytic processes with metals of the platinum group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/321—Catalytic processes
- C07C5/324—Catalytic processes with metals
- C07C5/325—Catalytic processes with metals of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a process for preparing catalysts containing at least one metal of the platinum group, in order to obtain more effective or performing catalysts in various types of reactions such as dehydrogenation, hydrogenation or dehydrocyclisation of hydrocarbons, more particularly for the dehydrogenation of paraffinic hydrocarbons having from 3 to 6 carbon atoms.
- the best known catalysts are constituted by an alumina support which is impregnated with a metallic compound of the tin group and with a metallic compound of the platinum group.
- the catalysts may also contain an alkaline or alkaline-earth promoter.
- the usual methods to prepare those catalysts comprise successive impregnations which are separated by either a drying step or a calcination step, although they sometimes consisted of a single impregnation step.
- the catalytic dehydrogenation of hydrocarbons may be achieved since many years and constitutes an important catalytic process in view of the increasing request for dehydrogenated products which may be valorized under various forms, such as gasolines having a high octane number, plastic materials and synthetic rubbers.
- LPG liquid petroleum gas
- the catalytic dehydrogenation of hydrocarbons is carried out in the presence of catalytic compositions containing platinum deposited on a support.
- the catalytic compositions may also contain other catalytically active metals such as tin or indium and promoters based on alkaline or alkaline-earth metals.
- the yield of the reaction at 600°C does not exceed about 30 to 35%, i.e. 70 to 81% with regard to the theoretical conversion, taking into account the thermodynamic constraints.
- the object of the present invention is to provide an improved process for preparing catalysts containing at least one metal of the platinum group and at least one metal of the tin group together with a promoter, said catalyst having a more important activity than similar catalysts prepared according to usual methods.
- Another object of the present invention is to provide an improved process for the dehydrogenation of paraffinic hydrocarbons having from 3 to 6 carbon atoms in the presence of a catalyst containing at least one metal selected from the group of platinum, a metal selected from the group of tin and a promoter.
- a further object of the present invention is to provide an improved process for the dehydrogenation of propane into propylene in the presence of a catalyst containing one or more metal selected from the platinum group, a metal selected from the tin group and a promoter of the alkaline or alkaline-earth metal type, the deposition of the one or more metal of the platinum group on the catalyst being carried out in two steps.
- the process of the present invention for the preparation of a catalyst consisting of an alumina support containing at least one metal from the platinum group together with a co-catalyst and a promoter comprises the step of submitting the alumina support, containing the co-catalyst and calcined at a temperature comprised between about 450 and about 550°C,
- the catalyst used in the present invention comprises an alumina support wherein are introduced at least a metal of the platinum group (as herein defined and referred to as the metal of the platinum group), a metal of the tin group (as herein defined and referred to as the metal of the tin group) and a promoter of the alkaline or alkaline-earth metal type (as herein defined and referred to as the promoter).
- the metal of the platinum group as herein defined, may be selected from the group consisting of platinum, palladium, rhenium, iridium, rhodium, osmium, ruthenium or mixtures thereof, platinum being preferred.
- the metal of the tin group may be selected from the group consisting of tin, germanium, lead or mixtures thereof, tin being preferred, which may be present as a compound such as the oxide.
- the promoter may be an alkaline metal selected from the group consisting of cesium, rubidium, potassium, sodium, lithium or mixtures thereof, or an alkaline-earth metal selected from the group consisting of baryum, strontium, calcium, magnesium or mixtures thereof, or even mixtures of alkaline and alkaline-earth metals, potassium being preferred; other promoters known to be efficient may also be envisaged.
- the alumina used as support generally has a specific area comprised between about 150 and 350 m2/g and a pore volume comprised between about 0.2 and 1.2 ml/g.
- the Applicant has unexpectedly found that the manner and the particular sequence of introduction of the catalytic metal compounds on the support, together with the conditions of intermediate calcination have an important influence on the catalyst activity in the scope of hydrocarbon dehydrogenation, hydrodrogenation or dehydrocyclisation reactions.
- a suitable catalyst is obtained for use in processes such as the dehydrogenation of paraffinic hydrocarbons having from 3 to 6 carbon atoms, the dehydrocyclisation of hydrocarbons having a straight chain of at least 6 carbon atoms, or the hydrogenation of unsaturated hydrocarbons.
- the alumina support is first impregnated with a compound of the metal of the tin group, in order to obtain a concentration of said metal in the final catalyst comprised between 0.1 and 2% by weight and preferably comprised between 0.15 and 1.0% by weight.
- tin As metal of the tin group, it is preferable to use tin.
- a slurry is formed from alumina and an aqueous solution of tin chloride. Said slurry is dried at a temperature of about 80 to 100°C. The alumina cake which contains the tin chloride is then pulverised and is finally formed into pellets which are then calcined at a temperature comprised between about 450 and about 550°C during 12 to 20 hours.
- the so-formed support is then treated so as to introduce therein a compound of the metal of the platinum group.
- the support is treated so as to deposit thereon, in a first step, a small fraction of the total amount of the metal of the platinum group which has to be finally present.
- the amount of metal of the platinum group which is deposited at this stage is comprised between about 10% and about 40% of the total amount of the metal of the platinum group.
- the deposition of said metal may be carried out by means of any suitable technique such as impregnation.
- the support is impregnated with an aqueous solution of chloroplatinic acid. After this impregnation, the newly impregnated support is submitted to a calcination at a temperature comprised between about 450 and about 550°C during 15 to 20 hours.
- the calcined support is submitted to a reduction under hydrogen atmosphere at a temperature also comprised between about 450 and about 550°C, during from about 1 to about 4 hours.
- this reduction step is very important and has a beneficial effect on the yield during the hydrogenation, dehydrogenation or dehydrocyclisation of hydrocarbons in the presence of this catalyst.
- the support Before carrying out a second treatment with the metal of the platinum group, the support is submitted to an intermediate treatment with a promoter.
- the alkaline or alkaline-earth metal is preferably well dispersed on the support.
- the amount of alkaline or alkaline-earth metal compound present on the support is comprised between about 0.5 and about 5% by weight and more particularly between about 0.8 and 2.5% by weight expressed as metal.
- potassium is most often deposited on the support in an amount corresponding to about 0.8 to about 2% by weight expressed as metal. It is believed that the promoter will generally be under the form of an oxide on the support rather than under its metallic form.
- the promoter may be deposited on the support in accordance with any suitable method such as impregnation. It is however preferred to deposit the promoter, preferably potassium, by impregnation of the support with an aqueous solution of its nitrate.
- the so-impregnated support is submitted to a calcination at a temperature comprised between about 380 and about 550°C in order to decompose the nitrate and to fix the oxide of alkaline or alkaline-earth metal on the support.
- a calcination is carried out in air during about 3 to 7 hours.
- the metal of the platinum group is finally deposited on the so-formed support in an amount sufficient to have a total content of said metal on the support comprised between about 0.1 and about 2% by weight, and preferably between about 0.2 and 1% by weight.
- the deposit of this metal may be carried out by means of any suitable technique such as impregnation. However at this stage of treatment of the support, the removal of the compounds which have already been deposited thereon must be avoided.
- an aqueous solution of a complex of platinum having the general formula (Pt L2)X2, (Pt L2)X4 or (Pt L4)X2, wherein L represents a ligand selected from NH3, R-NH2 or NH2-R-NH2, with R being an hydrocarbon radical having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, and wherein X represents NO3 or a halogen.
- An aqueous solution of the amminated complex having the formula (Pt(NH3)4)Cl2 is most preferably used.
- the newly impregnated support is dried then submitted to a calcination in air at a temperature comprised between about 450° and 525°C during about 10 to 20 hours.
- the so-prepared catalyst may be used in a hydrocarbon dehydrocyclisation, hydrogenation and dehydrogenation process without necessitating the use of other promoters to increase the stability or the selectivity.
- the catalytic dehydrogenation of paraffinic hydrocarbons is a preferred use of the catalysts prepared according to the invention.
- the process may be carried out in a fixed bed reactor or a mobile bed reactor or even a fluidised bed reactor; the process is most often carried out under continuous conditions, although it may also be carried out in batch.
- the hydrocarbon feed may be treated under the liquid form, or under a mixed phase liquid-vapour or also in vapour phase.
- the effluent from the reaction zone contains a part of unconverted feed, hydrogen and reaction products. This effluent is first cooled and sent into a separator to separate hydrogen and to recover a liquid phase which is then submitted to a series of separations in order to recover the desired product, and to recycle the unconverted phase to the reactor.
- a paraffinic hydrocarbon having from 3 to 6 carbon atoms preferably propane or any butane, most preferably propane
- the dehydrogenation process comprises the step of passing the feed to be dehydrogenated onto a catalyst prepared according to the invention, at a temperature comprised between about 400 and about 800°C, at a pressure comprised between about 1,013 and 1013,2 KPa (0.01 and 10 atm.) and at a weight hourly space velocity (WHSV) comprised between about 0.1 and 21.
- WHSV weight hourly space velocity
- the temperature is of about 530 to 650°C
- the pressure is comprised between about 50.6 and 303.9 KPa (0.5 and 3 atm.) and the WHSV is comprised between about 1 and about 10.
- the Applicant has unexpectedly found that by applying the process of the invention it becomes possible to considerably increase the yield of the dehydrogenation reaction when compared to the thermodynamic equilibrium, said yield being apt to exceed 90% when propane is dehydrogenated at a temperature of about 600°C.
- the feed may be diluted with usual gaseous diluents, under molar ratios most often comprised between 1 and 10 mole of diluent per mole of feed.
- gaseous diluents usually comprised between 1 and 10 mole of diluent per mole of feed.
- diluent N2, CO2 and H2O are the most often used.
- the Applicant has also found that it is more interesting to co-feed hydrogen with the feed under molar ratios generally comprised between 0.05 and 0.5 mole of hydrogen per mole of feed, whether or not the feed is also diluted with gaseous diluents.
- the catalyst prepared in accordance with the process of the invention is also suitable for the dehydrocyclization of straight chain acyclic hydrocarbons having in their structure a straight chain with at least 6 carbons atoms which may be cyclized.
- the preferred hydrocarbons are n-alkanes, although olefins may also be used.
- C6-C12 paraffins are generally used, and they will give benzene and/or lower alkyl aromatic compounds as the case may be, with a good yield and with a minimum of side reactions.
- the dehydrocyclization in the presence of the catalyst of the invention may be carried out under the following operating conditions:
- the hydrogenation process may be carried out under the following conditions:
- a 99.8% purity alumina having a specific area of 189 m2/g and a pore volume of 0.94 ml/g was used.
- This alumina was first impregnated with an aqueous solution of SnCl2. The impregnation was carried out in order to obtain a tin final content of 0.49% by weight. After this impregnation the support was calcined at 500°C during 18 hours.
- the tin containing support was then impregnated with a solution of H2PtCl6 in order to deposit about 0.15% platinum on the support.
- the support was then submitted to a further calcination at 500°C during 18 hours.
- the support was let in the oven at 500°C and hydrogen was passed on the support during 1 hour in order to carry out a reduction.
- the so-impregnated support was then treated with a solution of potassium nitrate in order to deposit thereon 1.00% by weight of potassium, expressed as metal.
- the support was then submitted to a calcination to fix the oxide of alkaline metal on the support; said calcination was carried out in air at 400°C during 5 hours.
- the second impregnation of the support with a platinum compound was carried out to obtain a platinum final content of 0.40% by weight.
- the support was contacted with an aqueous solution of platinum amminated complex of formula (Pt(NH3)4)Cl2. After the impregnation the support was calcined in air at 500°C during 18 hours.
- a propane feed was dehydrogenated by passing it through a reactor in the presence of the catalyst hereabove prepared, and under the following operating conditions:
- Hydrogen was co-fed with the feed under a molar ratio of 0.1 mole/mole of feed.
- Platinum has been deposited through two impregnations, but without carrying out any calcination or reduction after the first impregnation.
- Platium has been deposited on a Al2O3/Sn support in a single impregnation, without adding a promoter.
- the catatyst as prepared in Example 4 was used for the dehydrogenation of a n-butane feed under the following operating conditions.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
- The present invention relates to a process for preparing catalysts containing at least one metal of the platinum group, in order to obtain more effective or performing catalysts in various types of reactions such as dehydrogenation, hydrogenation or dehydrocyclisation of hydrocarbons, more particularly for the dehydrogenation of paraffinic hydrocarbons having from 3 to 6 carbon atoms.
- Many methods exist to prepare supported catalysts. In the present case, the best known catalysts are constituted by an alumina support which is impregnated with a metallic compound of the tin group and with a metallic compound of the platinum group. Generally, the catalysts may also contain an alkaline or alkaline-earth promoter. The usual methods to prepare those catalysts comprise successive impregnations which are separated by either a drying step or a calcination step, although they sometimes consisted of a single impregnation step.
- However, the so-formed catalysts are still not sufficiently performing, particularly when used in hydrocarbon hydrogenation or dehydrogenation processes.
- The catalytic dehydrogenation of hydrocarbons may be achieved since many years and constitutes an important catalytic process in view of the increasing request for dehydrogenated products which may be valorized under various forms, such as gasolines having a high octane number, plastic materials and synthetic rubbers.
- Moreover, in view of the increasing production of LPG (liquified petroleum gas), it seems particularly interesting to convert a part of those paraffinic hydrocarbons into dehydrogenated products such as propylene which is particularly interesting for the manufacture of plastic materials.
- The catalytic dehydrogenation of hydrocarbons is carried out in the presence of catalytic compositions containing platinum deposited on a support. The catalytic compositions may also contain other catalytically active metals such as tin or indium and promoters based on alkaline or alkaline-earth metals.
- Such processes and catalytic compositions have been described e.g. in US Patents 2,479,209, 2,602,772, 2,930,763, 3,531,543, 3,745,112, 3,892,657, 3,909,451 or still in US Patents 4,329,258, 4,363,721 and 4,430,517.
- Further, in most of these patents, it is also taught to use a halogen in order to improve the yield of the dehydrogenation reaction.
- However, despite all these already proposed developments, when they are applied to the dehydrogenation of propane, the yield of the reaction at 600°C does not exceed about 30 to 35%, i.e. 70 to 81% with regard to the theoretical conversion, taking into account the thermodynamic constraints.
- There is therefore a need to provide a process for preparing catalysts containing a metal of the platinum group and a metal of the tin group, which enables to obtain more active catalysts.
- The object of the present invention is to provide an improved process for preparing catalysts containing at least one metal of the platinum group and at least one metal of the tin group together with a promoter, said catalyst having a more important activity than similar catalysts prepared according to usual methods.
- Another object of the present invention is to provide an improved process for the dehydrogenation of paraffinic hydrocarbons having from 3 to 6 carbon atoms in the presence of a catalyst containing at least one metal selected from the group of platinum, a metal selected from the group of tin and a promoter.
- A further object of the present invention is to provide an improved process for the dehydrogenation of propane into propylene in the presence of a catalyst containing one or more metal selected from the platinum group, a metal selected from the tin group and a promoter of the alkaline or alkaline-earth metal type, the deposition of the one or more metal of the platinum group on the catalyst being carried out in two steps.
- The process of the present invention for the preparation of a catalyst consisting of an alumina support containing at least one metal from the platinum group together with a co-catalyst and a promoter comprises the step of submitting the alumina support, containing the co-catalyst and calcined at a temperature comprised between about 450 and about 550°C,
- to a first treatment with a compound of metal of the platinum group, said first treatment being followed by a calcination in air and by a reduction in the presence of hydrogen at a temperature comprised between 450 and 550°C;
- then to an intermediate treatment to deposit the promoter, said intermediate treatment being followed by a calcination at a temperature comprised between about 380 and about 550°C;
- and finally to a second treatment with a compound of metal of the platinum group, said second treatment being followed by a calcination at a temperature not exceeding 525°C,
- The catalyst used in the present invention comprises an alumina support wherein are introduced at least a metal of the platinum group (as herein defined and referred to as the metal of the platinum group), a metal of the tin group (as herein defined and referred to as the metal of the tin group) and a promoter of the alkaline or alkaline-earth metal type (as herein defined and referred to as the promoter). The metal of the platinum group, as herein defined, may be selected from the group consisting of platinum, palladium, rhenium, iridium, rhodium, osmium, ruthenium or mixtures thereof, platinum being preferred. The metal of the tin group, as herein defined, may be selected from the group consisting of tin, germanium, lead or mixtures thereof, tin being preferred, which may be present as a compound such as the oxide. The promoter may be an alkaline metal selected from the group consisting of cesium, rubidium, potassium, sodium, lithium or mixtures thereof, or an alkaline-earth metal selected from the group consisting of baryum, strontium, calcium, magnesium or mixtures thereof, or even mixtures of alkaline and alkaline-earth metals, potassium being preferred; other promoters known to be efficient may also be envisaged.
- The alumina used as support generally has a specific area comprised between about 150 and 350 m²/g and a pore volume comprised between about 0.2 and 1.2 ml/g.
- It is advisable to use an alumina having a purity higher than 98.5%, and in which the silica content does not exceed 1% while the iron content is lower than 0.1%.
- The Applicant has unexpectedly found that the manner and the particular sequence of introduction of the catalytic metal compounds on the support, together with the conditions of intermediate calcination have an important influence on the catalyst activity in the scope of hydrocarbon dehydrogenation, hydrodrogenation or dehydrocyclisation reactions.
- The Applicant has found that by applying the following sequence for the treatment of the alumina support, a suitable catalyst is obtained for use in processes such as the dehydrogenation of paraffinic hydrocarbons having from 3 to 6 carbon atoms, the dehydrocyclisation of hydrocarbons having a straight chain of at least 6 carbon atoms, or the hydrogenation of unsaturated hydrocarbons.
- The alumina support is first impregnated with a compound of the metal of the tin group, in order to obtain a concentration of said metal in the final catalyst comprised between 0.1 and 2% by weight and preferably comprised between 0.15 and 1.0% by weight.
- As metal of the tin group, it is preferable to use tin. According to an embodiment of the invention, a slurry is formed from alumina and an aqueous solution of tin chloride. Said slurry is dried at a temperature of about 80 to 100°C. The alumina cake which contains the tin chloride is then pulverised and is finally formed into pellets which are then calcined at a temperature comprised between about 450 and about 550°C during 12 to 20 hours.
- The so-formed support is then treated so as to introduce therein a compound of the metal of the platinum group. According to the present invention, the support is treated so as to deposit thereon, in a first step, a small fraction of the total amount of the metal of the platinum group which has to be finally present. Generally, the amount of metal of the platinum group which is deposited at this stage is comprised between about 10% and about 40% of the total amount of the metal of the platinum group. The deposition of said metal may be carried out by means of any suitable technique such as impregnation. Generally, when platinum is to be deposited, the support is impregnated with an aqueous solution of chloroplatinic acid. After this impregnation, the newly impregnated support is submitted to a calcination at a temperature comprised between about 450 and about 550°C during 15 to 20 hours.
- Thereafter, the calcined support is submitted to a reduction under hydrogen atmosphere at a temperature also comprised between about 450 and about 550°C, during from about 1 to about 4 hours.
- The Applicant has found that this reduction step is very important and has a beneficial effect on the yield during the hydrogenation, dehydrogenation or dehydrocyclisation of hydrocarbons in the presence of this catalyst.
- Before carrying out a second treatment with the metal of the platinum group, the support is submitted to an intermediate treatment with a promoter.
- The alkaline or alkaline-earth metal is preferably well dispersed on the support. Generally the amount of alkaline or alkaline-earth metal compound present on the support is comprised between about 0.5 and about 5% by weight and more particularly between about 0.8 and 2.5% by weight expressed as metal. Preferably selected, potassium is most often deposited on the support in an amount corresponding to about 0.8 to about 2% by weight expressed as metal. It is believed that the promoter will generally be under the form of an oxide on the support rather than under its metallic form.
- The promoter may be deposited on the support in accordance with any suitable method such as impregnation. It is however preferred to deposit the promoter, preferably potassium, by impregnation of the support with an aqueous solution of its nitrate.
- The so-impregnated support is submitted to a calcination at a temperature comprised between about 380 and about 550°C in order to decompose the nitrate and to fix the oxide of alkaline or alkaline-earth metal on the support. Generally the calcination is carried out in air during about 3 to 7 hours.
- According to the present invention, the metal of the platinum group is finally deposited on the so-formed support in an amount sufficient to have a total content of said metal on the support comprised between about 0.1 and about 2% by weight, and preferably between about 0.2 and 1% by weight. The deposit of this metal may be carried out by means of any suitable technique such as impregnation. However at this stage of treatment of the support, the removal of the compounds which have already been deposited thereon must be avoided. For this purpose, the Applicant has found that for this second impregnation of the metal of the platinum group, it is preferable to use an aqueous solution of a complex of platinum having the general formula (Pt L₂)X₂, (Pt L₂)X₄ or (Pt L₄)X₂, wherein L represents a ligand selected from NH₃, R-NH₂ or NH₂-R-NH₂, with R being an hydrocarbon radical having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, and wherein X represents NO₃ or a halogen. An aqueous solution of the amminated complex having the formula (Pt(NH₃)₄)Cl₂ is most preferably used.
- After this impregnation, the newly impregnated support is dried then submitted to a calcination in air at a temperature comprised between about 450° and 525°C during about 10 to 20 hours.
- According to the present invention, the so-prepared catalyst may be used in a hydrocarbon dehydrocyclisation, hydrogenation and dehydrogenation process without necessitating the use of other promoters to increase the stability or the selectivity. The catalytic dehydrogenation of paraffinic hydrocarbons is a preferred use of the catalysts prepared according to the invention.
- The process may be carried out in a fixed bed reactor or a mobile bed reactor or even a fluidised bed reactor; the process is most often carried out under continuous conditions, although it may also be carried out in batch. The hydrocarbon feed may be treated under the liquid form, or under a mixed phase liquid-vapour or also in vapour phase.
- The effluent from the reaction zone contains a part of unconverted feed, hydrogen and reaction products. This effluent is first cooled and sent into a separator to separate hydrogen and to recover a liquid phase which is then submitted to a series of separations in order to recover the desired product, and to recycle the unconverted phase to the reactor.
- In a dehydrogenation process, a feed of a paraffinic hydrocarbon having from 3 to 6 carbon atoms, preferably propane or any butane, most preferably propane, is contacted with the catalyst as hereabove described, under dehydrogenation operating conditions, generally in vapour phase.
- The dehydrogenation process comprises the step of passing the feed to be dehydrogenated onto a catalyst prepared according to the invention, at a temperature comprised between about 400 and about 800°C, at a pressure comprised between about 1,013 and 1013,2 KPa (0.01 and 10 atm.) and at a weight hourly space velocity (WHSV) comprised between about 0.1 and 21.
- More particularly, when propane is used as feed, the temperature is of about 530 to 650°C, the pressure is comprised between about 50.6 and 303.9 KPa (0.5 and 3 atm.) and the WHSV is comprised between about 1 and about 10.
- The Applicant has unexpectedly found that by applying the process of the invention it becomes possible to considerably increase the yield of the dehydrogenation reaction when compared to the thermodynamic equilibrium, said yield being apt to exceed 90% when propane is dehydrogenated at a temperature of about 600°C.
- The feed may be diluted with usual gaseous diluents, under molar ratios most often comprised between 1 and 10 mole of diluent per mole of feed. As diluent, N₂, CO₂ and H₂O are the most often used.
- The Applicant has also found that it is more interesting to co-feed hydrogen with the feed under molar ratios generally comprised between 0.05 and 0.5 mole of hydrogen per mole of feed, whether or not the feed is also diluted with gaseous diluents.
- The catalyst prepared in accordance with the process of the invention is also suitable for the dehydrocyclization of straight chain acyclic hydrocarbons having in their structure a straight chain with at least 6 carbons atoms which may be cyclized. The preferred hydrocarbons are n-alkanes, although olefins may also be used. C₆-C₁₂ paraffins are generally used, and they will give benzene and/or lower alkyl aromatic compounds as the case may be, with a good yield and with a minimum of side reactions.
- The dehydrocyclization in the presence of the catalyst of the invention may be carried out under the following operating conditions:
- Temperature:
- 300-650°C
- Pressure:
- 1-90 bar
- LHSV:
- 0.1-20
- Molar ratio H₂/HC:
- 0.5: 1 _ 10: 1 (HC = hydrocarbons)
- According to another aspect of the present invention, there is provided a process to transfer hydrogen onto insatured hydrocarbons, said process consisting in contacting hydrocarbons with hydrogen under conversion conditions in the presence of a catalyst as hereabove described.
- The hydrogenation process may be carried out under the following conditions:
- Temperature:
- 100-400°C
- Pressure:
- 1-90 bar
- LHSV:
- 0.1-20
- Molar ratio H₂/HC:
- 0.5: 1 _ 10: 1
- The following examples are given to better illustrate the process of the invention but without limiting its scope.
- A 99.8% purity alumina having a specific area of 189 m²/g and a pore volume of 0.94 ml/g was used.
- This alumina was first impregnated with an aqueous solution of SnCl₂. The impregnation was carried out in order to obtain a tin final content of 0.49% by weight. After this impregnation the support was calcined at 500°C during 18 hours.
- The tin containing support was then impregnated with a solution of H₂PtCl₆ in order to deposit about 0.15% platinum on the support. The support was then submitted to a further calcination at 500°C during 18 hours. The support was let in the oven at 500°C and hydrogen was passed on the support during 1 hour in order to carry out a reduction.
- The so-impregnated support was then treated with a solution of potassium nitrate in order to deposit thereon 1.00% by weight of potassium, expressed as metal.
- After this impregnation, the support was then submitted to a calcination to fix the oxide of alkaline metal on the support; said calcination was carried out in air at 400°C during 5 hours.
- Finally, the second impregnation of the support with a platinum compound was carried out to obtain a platinum final content of 0.40% by weight. To carry out this impregnation the support was contacted with an aqueous solution of platinum amminated complex of formula (Pt(NH₃)₄)Cl₂. After the impregnation the support was calcined in air at 500°C during 18 hours.
- A propane feed was dehydrogenated by passing it through a reactor in the presence of the catalyst hereabove prepared, and under the following operating conditions:
- Temperature:
- 600°C
- Pressure:
- 111.45 KPa (1.1 atm.)
- WHSV:
- 3
- Hydrogen was co-fed with the feed under a molar ratio of 0.1 mole/mole of feed.
- Propylene was recovered in the effluent with a yield of 91.1% of the thermodynamic equilibrium under these conditions.
- By way of comparison, different catalysts were prepared (Table I).
- Only one impregnation with platinum was carried out
- Only one impregnation with all the catalytic metals and the promoter was carried out
- A calcination and a reduction were carried out after the impregnation with platinum, but the second impregnation with platinum was not done.
- Platinum has been deposited through two impregnations, but without carrying out any calcination or reduction after the first impregnation.
- Platium has been deposited on a Al₂O₃/Sn support in a single impregnation, without adding a promoter.
-
-
- These catalysts were used for the dehydrogenation of a propane feed in accordance with the following operating conditions.
- T:
- 600°C
- Pressure:
- 1.1 atm (0.11 MPa)
- WHSV:
- 3
- H₂/HC:
- 0.1 mole/mole (HC = hydrocarbons)
-
- The catatyst as prepared in Example 4 was used for the dehydrogenation of a n-butane feed under the following operating conditions.
- T:
- 630°C
- Pressure:
- 2 atm (0.2 MPa)
- WHSV:
- 5
- H₂/HC:
- 0.4
-
- When a catalyst prepared as in the comparative example 1A, was used, a yield of only 48% was obtained with a selectivity of only 93.6%.
in order to obtain a catalyst containing from 0.1 to 2% by weight of at least one metal from the platinum group, from 0.1 to 2% by weight of at least one metal from the tin group as co-catalyst and from 0.5 to 5% by weight of at least one alkaline or alkaline-earth metal as promoter.
Claims (13)
in order to obtain a catalyst containing from 0.1 to 2% by weight of at least one metal from the platinum group, from 0.1 to 2% by weight of at least one metal from the tin group as co-catalyst and from 0.5 to 5% by weight of at least one alkaline or alkaline-earth metal as promoter.
the dehydrogenation being carried out in the presence of said catalyst at a temperature comprised between 530°C and 650°C, a pressure comprised between 50,6 and 303,9 kPa (0.5 and 3 atm.) and a weight hourly space velocity comprised between 1 and 10.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT89870026T ATE64551T1 (en) | 1988-02-11 | 1989-02-10 | PROCESSES FOR THE PREPARATION OF CATALYSTS CONTAINING PLATINUM GROUP METAL AND THEIR USES. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE8800158 | 1988-02-11 | ||
BE8800157A BE1002043A3 (en) | 1988-02-11 | 1988-02-11 | Paraffinic hydrocarbon catalytic dehydrogenation method |
BE8800158A BE1002425A4 (en) | 1988-02-11 | 1988-02-11 | Preparation method for catalysts containing a metal from the platinum group |
BE8800157 | 1988-02-11 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0328507A1 EP0328507A1 (en) | 1989-08-16 |
EP0328507B1 true EP0328507B1 (en) | 1991-06-19 |
Family
ID=25662345
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89870026A Expired - Lifetime EP0328507B1 (en) | 1988-02-11 | 1989-02-10 | Process for preparing catalysts containing a metal of the platinum group, and uses thereof |
Country Status (6)
Country | Link |
---|---|
US (2) | US4962265A (en) |
EP (1) | EP0328507B1 (en) |
AT (1) | ATE64551T1 (en) |
DE (1) | DE68900118D1 (en) |
ES (1) | ES2024072B3 (en) |
GR (1) | GR3002162T3 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101992086B (en) * | 2009-08-31 | 2013-01-09 | 中国石油化工股份有限公司 | Catalyst for producing alpha, alpha-dimethyl benzyl alcohol by hydrogenation of cumene hydroperoxide and preparation method thereof |
CN102218326B (en) * | 2010-04-15 | 2013-01-09 | 中国石油化工股份有限公司 | Oxide catalyst for producing Alpha-Alpha-dimethylphenyl carbinol and preparation method thereof |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0362960A3 (en) * | 1988-10-05 | 1990-06-27 | Sakai Chemical Industry Co., Ltd., | Use of a catalyst composition for denitrization and denitrizing catalysts |
IT1254988B (en) * | 1992-06-23 | 1995-10-11 | Eniricerche Spa | Process for the dehydrogenation of light paraffins in a fluidised bed reactor |
US5739074A (en) * | 1993-07-19 | 1998-04-14 | Uop | Metal cation-modified alkylation catalysts |
FR2713957B1 (en) * | 1993-12-16 | 1996-02-02 | Inst Francais Du Petrole | Paraffin dehydrogenation catalysts C3-C20 and its preparation. |
US5665668A (en) * | 1994-01-25 | 1997-09-09 | Grigorova; Bojidara | Method of making a catalyst |
IL112414A (en) * | 1994-01-25 | 1998-08-16 | Anglo American Res Lab Pty Ltd | Method of preparing a catalyst by impregnating a porous support with a solution |
US5482910A (en) * | 1994-07-05 | 1996-01-09 | Uop | Process for preparing a hydrocarbon conversion catalyst |
US5639929A (en) * | 1995-04-17 | 1997-06-17 | Regents Of The University Of Minnesota | Oxidative dehydrogenation process |
DE19535416A1 (en) * | 1995-09-23 | 1997-03-27 | Basf Ag | Process for the preparation of catalysts for selective dehydrogenation |
US5780701A (en) * | 1996-07-26 | 1998-07-14 | The Regents Of The University Of California | Process for alkane group dehydrogenation with organometallic catalyst |
US6074447A (en) * | 1997-02-21 | 2000-06-13 | University Of Hawaii | Hydrogen storage |
US6756339B1 (en) | 1998-04-01 | 2004-06-29 | Sud-Chemie Inc. | Dehydrogenation catalysts |
US6242379B1 (en) * | 1998-04-01 | 2001-06-05 | United Catalysts Inc. | Dehydrogenation catalysts |
US6602796B2 (en) | 1998-09-03 | 2003-08-05 | Micron Technology, Inc. | Chemical vapor deposition for smooth metal films |
CN106824186A (en) * | 2010-02-05 | 2017-06-13 | 埃克森美孚化学专利公司 | Cyclohexanone dehydrogenation and method |
US9242227B2 (en) | 2010-02-05 | 2016-01-26 | Exxonmobil Chemical Patents Inc. | Dehydrogenation catalyst and process |
CN102711988B (en) | 2010-02-05 | 2015-11-25 | 埃克森美孚化学专利公司 | Containing iridium catalyst, their preparation and purposes |
EP2712675A1 (en) | 2012-09-27 | 2014-04-02 | Saudi Basic Industries Corporation | Alkane dehydrogenation catalyst and process for its preparation |
US20150209759A1 (en) | 2012-07-26 | 2015-07-30 | Saudi Basic Industries Corporation | Alkane dehydrogenation catalyst and process for its preparation |
EP2689843A1 (en) | 2012-07-26 | 2014-01-29 | Saudi Basic Industries Corporation | Alkane dehydrogenation catalyst and process for its preparation |
US9676682B2 (en) * | 2013-09-10 | 2017-06-13 | Chevron U.S.A. Inc. | Catalyst complex and use thereof in alkane oligomerization |
CN111433175A (en) * | 2017-11-02 | 2020-07-17 | 环球油品有限责任公司 | Dehydrogenation process |
MX2020007463A (en) * | 2018-01-26 | 2020-09-14 | Clariant Corp | Dehydrogenation catalysts and methods for preparing and using them. |
US11760703B2 (en) | 2020-03-06 | 2023-09-19 | Exxonmobil Chemical Patents Inc. | Processes for upgrading alkanes and alkyl aromatic hydrocarbons |
CN115279721A (en) | 2020-03-06 | 2022-11-01 | 埃克森美孚化学专利公司 | Process for upgrading alkanes and alkylaromatics |
US11859136B2 (en) | 2020-03-06 | 2024-01-02 | Exxonmobil Chemical Patents Inc. | Processes for upgrading alkanes and alkyl aromatic hydrocarbons |
KR20220137724A (en) | 2020-03-06 | 2022-10-12 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | How to Upgrade Alkanes and Alkyl Aromatic Hydrocarbons |
CA3176347A1 (en) | 2020-05-08 | 2021-11-11 | Xiaoying Bao | Processes and systems for upgrading alkanes and alkyl aromatic hydrocarbons |
KR20230037036A (en) | 2020-08-06 | 2023-03-15 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Methods for Upgrading Alkanes and Alkyl Aromatic Hydrocarbons |
US20240190795A1 (en) | 2021-02-24 | 2024-06-13 | Fundació Eurecat | Alkane dehydrogenation nanocatalyst and process for its preparation |
KR20240005808A (en) | 2021-06-02 | 2024-01-12 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Methods for catalyst regeneration and alkane and/or alkyl aromatic hydrocarbon upgrading |
CA3227087A1 (en) | 2021-08-11 | 2023-02-16 | Christian A. DIAZ URRUTIA | Processes for dehydrogenating alkanes and alkyl aromatic hydrocarbons |
CA3228648A1 (en) | 2021-08-13 | 2023-02-16 | Exxonmobil Chemical Patents Inc. | Processes for dehydrogenating alkanes and alkyl aromatic hydrocarbons |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3649565A (en) * | 1969-10-20 | 1972-03-14 | Universal Oil Prod Co | Dehydrogenation method and catalytic composite for use therein |
US3880776A (en) * | 1971-06-10 | 1975-04-29 | Phillips Petroleum Co | Highly calcined support for catalytic dehydrogenation |
US3909451A (en) * | 1973-03-05 | 1975-09-30 | Universal Oil Prod Co | Dehydrogenation catalyst |
US4133839A (en) * | 1975-09-18 | 1979-01-09 | Uop Inc. | Dehydrogenation with a nonacidic multimetallic catalyst |
FR2457318A1 (en) * | 1979-05-22 | 1980-12-19 | Raffinage Cie Francaise | HYDROCARBON HYDROTREATMENT CATALYSTS AND APPLICATIONS OF SAID CATALYSTS |
US4409417A (en) * | 1982-07-26 | 1983-10-11 | Texaco Inc. | Process of dehydrogenation of hydrocarbons |
US4551574A (en) * | 1983-06-02 | 1985-11-05 | Uop Inc. | Indium-containing dehydrogenation catalyst |
US4684619A (en) * | 1985-02-20 | 1987-08-04 | The Dow Chemical Company | Process for making a dehydrogenation catalyst having improved moisture stability |
US4608360A (en) * | 1985-07-02 | 1986-08-26 | Uop Inc. | Dehydrogenation catalyst compositions and method of preparing same |
US4880764A (en) * | 1986-06-06 | 1989-11-14 | Uop | Dehydrogenation catalyst and process |
-
1989
- 1989-02-10 EP EP89870026A patent/EP0328507B1/en not_active Expired - Lifetime
- 1989-02-10 ES ES89870026T patent/ES2024072B3/en not_active Expired - Lifetime
- 1989-02-10 AT AT89870026T patent/ATE64551T1/en not_active IP Right Cessation
- 1989-02-10 DE DE8989870026T patent/DE68900118D1/en not_active Expired - Fee Related
- 1989-02-13 US US07/310,261 patent/US4962265A/en not_active Expired - Fee Related
-
1990
- 1990-05-03 US US07/519,183 patent/US5017543A/en not_active Expired - Fee Related
-
1991
- 1991-06-20 GR GR91400626T patent/GR3002162T3/en unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101992086B (en) * | 2009-08-31 | 2013-01-09 | 中国石油化工股份有限公司 | Catalyst for producing alpha, alpha-dimethyl benzyl alcohol by hydrogenation of cumene hydroperoxide and preparation method thereof |
CN102218326B (en) * | 2010-04-15 | 2013-01-09 | 中国石油化工股份有限公司 | Oxide catalyst for producing Alpha-Alpha-dimethylphenyl carbinol and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
GR3002162T3 (en) | 1992-12-30 |
US5017543A (en) | 1991-05-21 |
DE68900118D1 (en) | 1991-07-25 |
ES2024072B3 (en) | 1992-02-16 |
EP0328507A1 (en) | 1989-08-16 |
ATE64551T1 (en) | 1991-07-15 |
US4962265A (en) | 1990-10-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0328507B1 (en) | Process for preparing catalysts containing a metal of the platinum group, and uses thereof | |
US4899012A (en) | Catalyst for the isomerization of aromatics | |
US2900425A (en) | Isomerization process | |
US6426442B1 (en) | Catalyst for the conversion of low carbon number aliphatic hydrocarbons to higher carbon number hydrocarbons, process for preparing the catalyst and process using the catalyst | |
EP0212850B1 (en) | Dehydrogenation process and catalyst | |
US3511888A (en) | Paraffin conversion catalyst and process | |
US5284986A (en) | Upgrading of normal pentane to cyclopentene | |
US5138112A (en) | Process for converting a C2 -C6 aliphatic hydrocarbon to high octane transportable fuel | |
US4548918A (en) | Process for manufacturing a hydrocarbon conversion catalyst and catalyst prepared by said process | |
US4982047A (en) | Chemical process and catalyst | |
US5254787A (en) | Dehydrogenation and dehydrocyclization using a non-acidic NU-87 catalyst | |
US3760029A (en) | Dimethylsulfide removal in the isomerization of normal paraffins | |
US5189234A (en) | Selective dehydrogenation processes and catalysts | |
US2848510A (en) | Manganese reforming oxide-containing catalyst | |
US3642925A (en) | Hydrocarbon isomerization process | |
US5446230A (en) | Chlorinated, alumina-based, bimetallic catalyst and its use in the isomerization of C4 -C6 paraffins | |
US3078318A (en) | Production of specific xylene isomers | |
GB2091754A (en) | Aromatic hydrocarbons from paraffins | |
US4798911A (en) | Catalyst composition and method for selective dehydrogenation | |
JP2593334B2 (en) | Method for isomerizing 1-butene to 2-butene in C4 hydrocarbon fraction containing butadiene and sulfur compounds | |
US4072731A (en) | Dehydrocyclization with an acidic multimetallic catalytic composite | |
US3630961A (en) | Hydrocarbon isomerization process | |
EP0390058B1 (en) | Catalyst composition, process for cracking non-aromatic hydrocarbons and process for isomerizing c8 aromatic hydrocarbons | |
US3723554A (en) | Hydrocarbon isomerization process | |
US3662018A (en) | Process of improving the selectivity of dehydrogenation catalysts |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
17P | Request for examination filed |
Effective date: 19890804 |
|
17Q | First examination report despatched |
Effective date: 19900718 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: FINA RESEARCH S.A. |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
REF | Corresponds to: |
Ref document number: 64551 Country of ref document: AT Date of ref document: 19910715 Kind code of ref document: T |
|
ET | Fr: translation filed | ||
REF | Corresponds to: |
Ref document number: 68900118 Country of ref document: DE Date of ref document: 19910725 |
|
ITF | It: translation for a ep patent filed |
Owner name: UFFICIO BREVETTI RICCARDI & C. |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2024072 Country of ref document: ES Kind code of ref document: B3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GR Ref legal event code: FG4A Free format text: 3002162 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 19930121 Year of fee payment: 5 |
|
EPTA | Lu: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GR Payment date: 19940127 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19940210 |
|
EAL | Se: european patent in force in sweden |
Ref document number: 89870026.5 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19950831 |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: MM2A Free format text: 3002162 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20010112 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20010115 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20010116 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20010123 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20010124 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20010205 Year of fee payment: 13 Ref country code: FR Payment date: 20010205 Year of fee payment: 13 Ref country code: DE Payment date: 20010205 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20010220 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020210 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020210 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020211 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020211 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020228 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020228 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020228 |
|
BERE | Be: lapsed |
Owner name: S.A. FINA RESEARCH Effective date: 20020228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020901 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020903 |
|
EUG | Se: european patent has lapsed |
Ref document number: 89870026.5 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20020210 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021031 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20020901 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050210 |